Reactive colorants, mixtures of reactive colorants and production and use thereof

ABSTRACT

Dyes of formula (1)                    
     wherein 
     R 1  and R 2  are each independently of the other hydrogen or C 1 -C 4 alkyl, and 
     D 1  and D 2  are each independently of the other a radical of formula (2)                    
      wherein 
     (R 3 ) 0-3  denotes from 0 to 3 identical or different substituents selected from the group halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, nitro and sulfo, and 
     X 1  is a radical of formula (3 a ), (3 b ), (3 c ), (3 d ), (3 e ) or (3 f ) 
     
       
         —SO 2 —Z  (3 a ), 
       
     
     
       
         —NH—CO—(CH 2 ) m —SO 2 —Z  (3 b ), 
       
     
     
       
         —CONH—(CH 2 ) n —SO 2 —Z  (3 c ), 
       
     
     
       
         —NH—CO—CH(Hal)-CH 2 -Hal  (3 d ), 
       
     
     
       
         —NH—CO—C(Hal)=CH 2   (3 e ) 
       
     
     or                    
      wherein 
     Y is halogen, T independently thereof has a meaning given for Y or is a non-fiber-reactive substituent or is a fiber-reactive radical of formula (4 a ), (4 b ), (4 c ), (4 d ) or (4 e ) 
     
       
         —NH—(CH 2 ) 2-3 —SO 2 —Z  (4 a ), 
       
     
     
       
         —NH—(CH 2 ) 2-3 —O—(CH 2 ) 2-3 —SO 2 —Z  (4 b ),  
       
       
         
         
             
             
         
       
     
      wherein 
     Z is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions, 
     Z′ is a group —CH(Hal)-CH 2 -Hal or —C(Hal)=CH 2 , 
     m and n are each independently of the other the number 2, 3 or 4, and 
     Hal is halogen, 
     are suitable for dyeing a wide variety of fiber materials, especially cellulosic fiber materials, and yield dyeings having good allround properties.

The present invention relates to novel reactive colorants and mixtures of reactive colorants, to processes for their production and to their use.

The practice of dyeing using reactive dyes has recently led to higher demands being made of the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.

Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.

The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes and mixtures of reactive dyes that possess the qualities characterised above to a high degree. The novel dyes and dye mixtures should especially be distinguished by high fixing yields and high fibre-dye binding stability; it should also be possible for dye that is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good allround properties, for example fastness to light and to wetting.

It has been shown that the problem posed is largely solved by the novel dyes and dye mixtures defined below.

The present invention accordingly relates to dyes of formula (1)

wherein

R₁ and R₂ are each independently of the other hydrogen or C₁-C₄alkyl, and

D₁ and D₂ are each independently of the other a radical of formula (2)

 wherein

(R₃)₀₋₃ denotes from 0 to 3 identical or different substituents selected from the group halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, nitro and sulfo, and

X₁ is a radical of formula (3a), (3b), (3c), (3d), (3e) or (3f)

—SO₂—Z  (3a),

—NH—CO—(CH₂)_(m)—SO₂—Z  (3b),

—CONH—(CH₂)_(n)—SO₂—Z  (3c),

—NH—CO—CH(Hal)—CH₂—Hal  (3d),

—NH—CO—C(Hal)═CH₂  (3e) or

 wherein

Y is halogen, T independently thereof has a meaning given for Y or is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e)

—NH—(CH₂)₂₋₃—SO₂—Z  (4a),

 —NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂—Z  (4b),

 wherein

Z is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions,

Z′ is a group —CH(Hal)—CH₂—Hal or —C(Hal)═CH₂,

m and n are each independently of the other the number 2, 3 or 4, and

Hal is halogen.

As C₁-C₄alkyl for R₁ and R₂, each independently of the other, there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, especially methyl and ethyl.

Preferably, one of the radicals R₁ or R₂ is hydrogen and the other is methyl or ethyl.

Special preference is given to R₁ and R₂ as hydrogen.

As halogen for R₃ there come into consideration, for example, fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and especially chlorine.

As C₁-C₄alkyl for R₃ there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, preferably methyl and ethyl, and especially methyl.

As C₁-C₄alkoxy for R₃ there come into consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy, preferably methoxy and ethoxy, and especially methoxy.

Preferably, T is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e).

If T is a non-fibre-reactive substituent, it may be, for example, hydroxy; C₁-C₄alkoxy; unsubstituted or hydroxy-, carboxy- or sulfo-substituted C₁-C₄alkylthio; amino; amino mono- or di-substituted by C₁-C₈alkyl, wherein the alkyl is unsubstituted or is further substituted, e.g. by sulfo, sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or by hydroxy and is uninterrupted or interrupted by an —O— radical; cyclohexylamino; morpholino; N—C₁-C₄alkyl-N-phenylamino or phenylamino or naphthylamino, wherein the phenyl or naphthyl is unsubstituted or substituted, e.g. by C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, sulfo or by halogen.

Examples of suitable non-fibre-reactive substituents T include amino, methylamino, ethylamino, β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As non-fibre-reactive radical, T is preferably C₁-C₄alkoxy, unsubstituted or hydroxy-, carboxy- or sulfo-substituted C₁-C₄alkylthio, hydroxy, amino, N-mono- or N,N-di-C₁-C₄-alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, or phenylamino or N—C₁-C₄alkyl-N-phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato) wherein the phenyl ring is in each case unsubstituted or substituted by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals T are amino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or N—C₁-C₄alkyl-N-phenylamino.

In the case of the fibre-reactive radicals T of formulae (4a) and (4b), Z is preferably β-chloroethyl. In the case of the fibre-reactive radicals T of formulae (4c) and (4d), Z is preferably vinyl or β-sulfatoethyl.

If T is a fibre-reactive radical, T is preferably a radical of formula (4c) or (4d), and especially of formula (4c).

Hal in the fibre-reactive radicals of formulae (3d), (3e) and (4e) is preferably chlorine or bromine, especially bromine.

Y in the fibre-reactive radical of formula (3f) is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and especially chlorine.

As a leaving group U there come into consideration, for example, —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl and —OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group of formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially —Cl or —OSO₃H, and more especially —OSO₃H.

Examples of suitable radicals Z accordingly include vinyl, β-bromo- or β-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thiosulfatoethyl. Z is preferably vinyl, β-chloroethyl or β-sulfatoethyl.

D₁ and D₂ preferably are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e)

especially of formula (2a) or (2e), wherein

(R_(3a))₀₋₂ denotes from 0 to 2 identical or different substituents selected from the group halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, especially methyl, methoxy and sulfo,

X_(1a) is α,β-dibromopropionylamino or α-bromoacryloylamino,

m is the number 2 or 3, especially 3,

n is the number 2 or 3, especially 2, and

Z₁, Z₂, Z₃ and Z₄ are each independently of the others vinyl, β-chloroethyl or β-sulfatoethyl.

Z₁ and Z₂ are preferably each independently of the other vinyl or β-sulfatoethyl.

Z₃ is preferably β-chloroethyl or β-sulfatoethyl, especially β-chloroethyl.

Z₄ is preferably β-chloroethyl or β-sulfatoethyl, especially β-sulfatoethyl.

Preference is given to dyes of formula (1) wherein

D₁ and D₂ are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e), preferably of formula (2a) or (2e), and

R₁ and R₂ are hydrogen.

The radicals D₁ and D₂ in the dyes of formula (1) are identical or not identical.

The present invention relates also to a process for the preparation of dyes of formula (1), wherein

(i) approximately 1 molar equivalent of an amine of formula (5a)

D₁—NH₂  (5a)

is diazotised in customary manner and reacted with approximately 1 molar equivalent of a compound of formula (6)

 to form the compound of formula (7a)

 and

(ii) approximately 1 molar equivalent of an amine of formula (5b)

 D₂—NH₂  (5b)

is diazotised in customary manner and reacted with approximately 1 molar equivalent of the compound of formula (7a) obtained according to (i), to form the compound of formula (1) wherein the definitions and preferred meanings given above for each of D₁, D₂, R₁ and R₂ apply.

The diazotisation of the amines of formulae (5a) and (5b) is carried out in a manner known per se, for example with a nitrite, e.g. with an alkali metal nitrite, such as sodium nitrite, in a mineral acid medium, e.g. in a hydrochloric acid medium, at temperatures of, for example, from −5 to 40° C., preferably from 0 to 20° C.

Coupling to the coupling components of formulae (6) and (7a) is carried out in a manner known per se, at acid, neutral or weakly alkaline pH values, for example at a pH value of from 0 to 8, and at temperatures of, for example, from −5 to 40° C., preferably from 0 to 30° C.

The first coupling (i) is effected in an acid medium, for example at a pH value of from 0 to 4, and the second coupling (ii) is effected at a higher pH value, in a weakly acid, neutral or weakly alkaline medium, for example at a pH value of from 4 to 8.

If the same procedure as described above is used, except that, instead of using 1 molar equivalent of an amine of formula (5a) and 1 molar equivalent of an amine of formula (5b), there are used in each of the process steps (i) and (ii) approximately 1 molar equivalent of a mixture of at least two, but preferably two, non-identical amines, for example a 1:1 molar mixture of the compounds of formulae (5a) and (5b), there are then obtained first, according to (i), a mixture of the compounds of formulae (7a) and (7b)

and, on further reaction of the mixture of the compounds of formulae (7a) and (7b), according to (ii), a mixture of dyes of formulae (1a), (1b), (1c) and (1d)

The present invention accordingly relates also to dye mixtures comprising at least one dye of formulae (1a) and (1b) together with at least one dye of formulae (1c) and (1d), especially one dye of each of formulae (1a), (1b), (1c) and (1d), wherein the definitions and preferred meanings given above for each of D₁, D₂, R₁ and R₂ apply and D₁ and D₂ are not identical.

Preferably, in the dye mixtures according to the invention, D₁ is a radical of formula (2a*)

and D₂ is a radical of formula (2a**)

wherein

R_(3b) and R_(3c) are each independently of the other hydrogen, methyl or methoxy, especially hydrogen, and

Z_(1a) and Z_(1b) are each independently of the other vinyl or β-sulfatoethyl, especially β-sulfatoethyl, and

R₁ and R₂ are hydrogen.

The ratio of the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture can vary within wide ranges and will depend upon the ratio of the amines D₁—NH₂ and D₂—NH₂ used according to each of (i) and (ii).

The dye mixtures mentioned above contain, for example, from 5 to 95% by weight, especially from 10 to 90% by weight, and more especially from 20 to 80% by weight, of a dye of formula (1a) and/or (1b), based on the total amount of the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture.

The compounds of formulae (5a), (5b) and (6) are known or can be obtained in a manner known per se.

The present invention relates also to dye mixtures comprising at least one dye of formula (1) together with at least one dye of formula (8)

wherein

r and s are each independently of the other the number 0 or 1 and

X₂ and X₃ are each independently of the other a radical of formula (3a), (3b), (3c) or (3d)

—SO₂—Z  (3a),

—CONH—(CH₂)_(n)—SO₂—Z  (3b),

—NH—CO—CH(Hal)—CH₂—Hal  (3c)

or

—NH—CO—C(Hal)═CH₂  (3d),

 and

n is the number 2, 3 or 4,

Hal is halogen and

Z is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions.

The definitions and preferred meanings given above for each of n, Hal and U apply.

The reactive dyes of formulae (1) and (8) contain sulfo groups, which may in each case be present either in the form of the free sulfo acid or, preferably, in the form of a salt thereof, for example in the form of a sodium, lithium, potassium or ammonium salt or in the form of a salt of an organic amine, e.g. in the form of a triethanolammonium salt.

The reactive dyes of formulae (1) and (8) and accordingly the dye mixtures may also comprise further additives, for example sodium chloride or dextrin.

Instead of the dye of formula (1), the dye mixtures according to the invention preferably comprise the above-mentioned mixtures of at least one dye of formulae (1a) and (1b) together with at least one dye of formulae (1c) and (1d), especially a compound of each of formulae (1a), (1b), (1c) and (1d), wherein the definitions and preferred meanings given above for the radicals D₁, D₂, R₁ and R₂ in the compounds of formulae (1a), (1b), (1c) and (1d) apply.

The dye of formula (8) in the dye mixture according to the invention is preferably a dye of formula (8a), (8b) or (8c)

especially of formula (8a),

wherein

one of the substituents G₁ and G₂ is amino and the other is hydroxy,

X_(2a), X_(3a) and X_(3b) are each independently of the others β-sulfatoethylsulfonyl or vinylsulfonyl and

X_(2b), X_(2c) and X_(3c) are each independently of the others α,β-dibromopropionylamino or α-bromoacryloylamino.

Especially preferred dye mixtures according to the invention comprise a compound of each of formulae (1a), (1b), (1c) and (1d) together with a dye of formula (8a).

The dye of formula (1) or the dyes of formulae (1a), (lb), (1c) and (1d) are present in the dye mixture according to the invention in a weight ratio with respect to the dye of formula (8) of, for example, from 1:99 to 99:1, preferably from 5:95 to 95:5, and especially from 10:90 to 90:10.

The dye mixtures according to the invention may be prepared, for example, by mixing the individual dyes. The mixing process is carried out, for example, in a suitable mill, e.g. a ball or pin mill, and also in a kneader or mixer.

The dye mixtures according to the invention may comprise, in addition to the reactive dyes mentioned above, further dyes, especially further reactive dyes for shade adjustment.

The dyes and dye mixtures according to the invention are fibre-reactive, that is they are capable of reacting with the hydroxyl groups of cellulose or with the reactive centres of natural and synthetic polyamides, with the formation of covalent chemical bonds.

The reactive dyes according to the invention and the mixtures of reactive dyes according to the invention are suitable for dyeing and printing a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials. Examples include silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes and dye mixtures according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres contained in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.

The dyes and dye mixtures according to the invention can be applied to the fibre material and fixed to the fibre in a number of ways, especially in the form of aqueous dye solutions or dye print pastes. They are suitable for the exhaust process and also for dyeing using the pad-dyeing process, can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The dyes and dye mixtures according to the invention are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics containing wool.

The dyeings and prints produced on cellulose fibre materials using the dyes and dye mixtures according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both acidic and alkaline ranges, and they also have good fastness to light and very good wet-fastness properties, such as fastness to washing, water, seawater, cross-dyeing and to perspiration, as well as good fastness to pleating, to pressing, to rubbing, and especially to chlorine.

The following Examples serve to illustrate the invention. The temperatures are given in degrees Celsius, parts are parts by weight, and the percentages relate to percent by weight, unless otherwise indicated. Parts by weight relate to parts by volume in a ratio of kilograms to liters.

EXAMPLE 1

28.1 parts of an amine of formula D₁₀—NH₂, wherein D₁₀ is a radical of formula

are added to 200 parts of water and stirred thoroughly. At about from 10 to 20° C., 17 parts of concentrated hydrochloric acid are added to the resulting suspension, the mixture is cooled to from 0 to 5° C., and 6.9 parts of sodium nitrite dissolved in 25 parts of water are slowly added dropwise. When the conversion of the amine to the corresponding diazo compound is complete, the excess of nitrite is destroyed by the addition of sulfamic acid.

EXAMPLE 2

36.2 parts of an amine of formula D₁₁—NH₂, wherein D₁₁ is a radical of formula

are added to 400 parts of water and stirred thoroughly. At about from 10 to 20° C., 29 parts of concentrated hydrochloric acid are added to the resulting suspension, the mixture is cooled to from 0 to 5° C., and 6.2 parts of sodium nitrite dissolved in 22.5 parts of water are slowly added dropwise. When the conversion of the amine to the corresponding diazo compound is complete, the excess of nitrite is destroyed by the addition of sulfamic acid.

EXAMPLES 3 TO 17

The diazo compounds of the amines given in Table 1 can be prepared analogously to the procedure described in Examples 1 and 2 by using, instead of the amines of formula D₁₀—NH₂ or D₁₁—NH₂ mentioned in Example 1 or 2, an equimolar amount of the amines of formula D_(xy)—NH₂ given in Table 1.

TABLE 1 Amine Ex. D_(xy)-NH₂ D_(xy) 3 D₁₂-NH₂

4 D₁₃-NH₂

5 D₁₄-NH₂

6 D₁₅-NH₂

7 D₁₆-NH₂

8 D₁₇-NH₂

9 D₁₈-NH₂

10 D₁₉-NH₂

11 D₂₀-NH₂

12 D₂₁-NH₂

13 D₂₂-NH₂

14 D₂₃-NH₂

15 D₂₄-NH₂

16 D₂₅-NH₂

17 D₂₅-NH₂

18 D₂₇-NH₂

19 D₂₈-NH₂

20 D₂₉-NH₂

21 D₃₀-NH₂

22 D₃₁-NH₂

23 D₃₂-NH₂

24 D₃₃-NH₂

25 D₃₄-NH₂

EXAMPLE 26

A solution of 21.5 parts of 2-amino-5-naphthol-7-sulfonic acid in 250 parts of water (pH 7) are added dropwise, at from 0 to 5° C., to the acidic suspension of the diazo compound obtained according to Example 1. The mixture is allowed to warm up to room temperature and is stirred for about 5 hours until coupling is complete (first coupling). The reaction mixture is then cooled to from 5 to 10° C., the pH value is raised to about 4.5 using aqueous sodium hydrogen carbonate solution and the suspension of diazo compound obtained according to Example 2 is slowly added dropwise, the pH value being maintained at about 4.5 during the dropwise addition by the addition of aqueous sodium hydrogen carbonate solution and the temperature being maintained at about 5° C. After the dropwise addition, the pH value is adjusted to 6 (second coupling). When coupling is complete, the dye solution is freed of salt by dialysis and concentrated by evaporation in vacuo to obtain a compound that in the form of the free acid corresponds to formula (101)

and dyes cellulose a scarlet shade with good allround properties.

EXAMPLE 27

Following a procedure analogous to that described in Example 26 but using, for the second coupling, an equimolar amount of the diazotised amine according to Example 1 instead of the diazotised amine according to Example 2, there is obtained a compound that in the form of the free acid corresponds to formula (102)

and dyes cellulose a scarlet shade with good allround properties.

EXAMPLES 28 TO 86

From the diazo compounds described in Examples 1 to 25 there can be prepared, analogously to the procedure described in Example 26 or 27, dyes of the following general formula

wherein D¹ _(xy) and D² _(xy) correspond to the particular radicals set out in Table 2 and those radicals are as defined in Table 1. The dyes dye cellulose the shades given in Table 2 with good allround properties.

TABLE 2 D¹ _(xy) D² _(xy) Ex. first coupling second coupling Shade 28 D11 D₁₁ scarlet 29 D₁₂ D₁₂ scarlet 30 D₁₃ D₁₃ scarlet 31 D₁₄ D₁₄ scarlet 32 D₁₅ D₁₅ scarlet 33 D₁₆ D₁₆ scarlet 34 D₁₇ D₁₇ scarlet 35 D₁₈ D₁₈ scarlet 36 D₁₉ D₁₉ scarlet 37 D₂₀ D₂₀ scarlet 38 D₂₁ D₂₁ scarlet 39 D₂₂ D₂₂ scarlet 40 D₂₃ D₂₃ scarlet 41 D₂₄ D₂₄ scarlet 42 D₂₅ D₂₅ scarlet 43 D₂₆ D₂₆ scarlet 44 D₁₀ D₁₂ scarlet 45 D₁₂ D₁₀ scarlet 46 D₁₀ D₁₃ scarlet 47 D₁₃ D₁₀ scarlet 48 D₁₀ D₂₀ scarlet 49 D₁₃ D₂₁ scarlet 50 D₂₁ D₁₃ scarlet 51 D₁₀ D₁₄ scarlet 52 D₁₀ D₁₅ scarlet 53 D₁₀ D₁₆ scarlet 54 D₁₀ D₁₇ scarlet 55 D₁₀ D₁₈ scarlet 56 D₁₀ D₁₉ scarlet 57 D₁₀ D₂₁ scarlet 58 D₁₀ D₂₂ scarlet 59 D₁₀ D₂₃ scarlet 60 D₁₀ D₂₄ scarlet 61 D₁₀ D₂₅ scarlet 62 D₁₀ D₂₆ scarlet 63 D₁₃ D₂₀ scarlet 64 D₁₃ D₂₂ scarlet 65 D₁₄ D₁₁ scarlet 66 D₂₉ D₃₂ scarlet 67 D₂₉ D₃₀ scarlet 68 D₂₉ D₁₀ scarlet 69 D₂₉ D₃₁ scarlet 70 D₃₃ D₃₃ scarlet 71 D₂₈ D₂₈ scarlet 72 D₂₈ D₂₇ scarlet 73 D₁₀ D₂₉ scarlet 74 D₁₀ D₃₁ scarlet 75 D₁₁ D₃₁ scarlet 76 D₃₁ D₁₁ scarlet 77 D₃₃ D₁₁ scarlet 78 D₃₄ D₃₄ scarlet 79 D₂₁ D₃₄ scarlet 80 D₃₄ D₂₁ scarlet 81 D₃₄ D₁₀ scarlet 82 D₁₀ D₃₄ scarlet 83 D₃₁ D₃₁ scarlet 84 D₁₀ D₃₃ scarlet 55 D₁₃ D₃₂ scarlet 86 D₁₉ D₂₁ scarlet

EXAMPLE 87

A mixture of 14.1 parts of an amine of formula D₁₀—NH₂ and 18.1 parts of an amine of formula D₁₃—NH₂, wherein D₁₀ and D₁₃ are as defined in Example 1 and in Table 1, respectively, is added to 200 parts of water and stirred thoroughly. At about from 10 to 20° C., 17 parts of concentrated hydrochloric acid are added to the resulting suspension, the mixture is cooled to from 0 to 5° C., and 6.9 parts of sodium nitrite dissolved in 25 parts of water are slowly added dropwise. When the conversion of the amines to the corresponding diazo compounds is complete, the excess of nitrite is destroyed by the addition of sulfamic acid.

EXAMPLE 88

A solution of 21.5 parts of 2-amino-5-naphthol-7-sulfonic acid in 250 parts of water (pH 7) is added dropwise, at from 0 to 5° C., to the acidic suspension of the diazo compounds obtained according to Example 87. The mixture is allowed to warm up to room temperature and is stirred for about 5 hours until coupling is complete. The reaction mixture is then cooled to from 5 to 10° C., the pH value is raised to about 4.5 using aqueous sodium hydrogen carbonate solution and the suspension of diazo compounds obtained according to Example 87 is again slowly added dropwise, the pH being maintained at about 4.5 during the dropwise addition by the addition of aqueous sodium hydrogen carbonate solution and the temperature being maintained at about 5° C. After the dropwise addition, the pH value is adjusted to 6. When coupling is complete, the dye solution is freed of salt by dialysis and concentrated by evaporation in vacuo to obtain a mixture of compounds that in the form of their free acids correspond to formulae (103), (104), (105)

and (102) and dye cellulose a scarlet shade with good allround properties.

EXAMPLES 89 TO 123

From 1:1 molar mixtures of, in each case, two different amines of formulae D¹ _(xy)—NH₂ and D² _(xy)—NH₂ there can be prepared, analogously to the procedure described in Example 87, the corresponding diazo compounds and from those diazo compounds there can be obtained, analogously to the procedure described in Example 88, mixtures of dyes of the following general formulae

wherein D¹ _(xy) and D² _(xy) correspond to the radicals listed in each case in Table 3, those radicals being as defined in Table 1. The dyes dye cellulose the shades given in Table 3 with good allround properties.

TABLE 3 Ex. D¹ _(xy) D² _(xy) Shade 89 D₁₀ D₁₂ scarlet 90 D₁₀ D₁₄ scarlet 91 D₁₀ D₁₅ scarlet 92 D₁₀ D₁₆ scarlet 93 D₁₀ D₁₇ scarlet 94 D₁₀ D₁₈ scarlet 95 D₁₀ D₁₉ scarlet 96 D₁₀ D₂₀ scarlet 97 D₁₀ D₂₁ scarlet 98 D₁₀ D₂₂ scarlet 99 D₁₀ D₂₃ scarlet 100 D₁₀ D₂₄ scarlet 101 D₁₀ D₂₅ scarlet 102 D₁₀ D₂₆ scarlet 103 D₁₁ D₁₂ scarlet 104 D₁₁ D₁₃ scarlet 105 D₁₁ D₁₄ scarlet 106 D₁₁ D₁₉ scarlet 107 D₁₁ D₂₀ scarlet 108 D₁₂ D₁₃ scarlet 109 D₁₂ D₂₃ scarlet 110 D₁₃ D₁₄ scarlet 111 D₁₃ D₁₉ scarlet 112 D₁₃ D₂₀ scarlet 113 D₁₃ D₂₁ scarlet 114 D₁₃ D₂₂ scarlet 115 D₁₄ D₁₇ scarlet 116 D₁₄ D₁₈ scarlet 117 D₁₄ D₁₉ scarlet 118 D₁₄ D₂₀ scarlet 119 D₁₄ D₂₁ scarlet 120 D₁₄ D₂₃ scarlet 121 D₁₄ D₂₄ scarlet 122 D₁₇ D₁₉ scarlet 123 D₁₈ D₁₉ scarlet

DYEING EXAMPLE 124

100 parts of cotton fabric are placed in a dye bath at a temperature of 30° C. containing 0.75 part of the dye mixture according to Example 88, 0.75 part of the dye of formula (106)

and 3.5 parts of the dye of formula (107)

and 30 parts of sodium chloride in 1000 parts of water. The temperature of the dyebath is raised to 90° C. over a period of 30 minutes and maintained for a further 45 minutes. The temperature is then reduced to 70° C. over a period of about 15 minutes, 15 parts of calcined soda are added and the temperature of the dyebath is maintained at 70° C. for a further 45 minutes. The dyed fabric is then, in customary manner, rinsed and dried. A cotton fabric dyed black is obtained, which has good allround properties.

Dyeing Procedure I

2 parts of the dye obtained according to Example 26 are dissolved in 400 parts of water; 1500 parts of a solution containing 53 g of sodium chloride per liter are added. 100 parts of cotton fabric are placed in the dyebath at 40° C. After 45 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of calcined soda per liter are added. The temperature of the dyebath is maintained at 40° C. for a further 45 minutes. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing Procedure II

2 parts of the reactive dye obtained according to Example 26 are dissolved in 400 parts of water; 1500 parts of a solution containing 53 g of sodium chloride per liter are added. 100 parts of cotton fabric are placed in the dyebath at 35° C. After 20 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of calcined soda per liter are added. The temperature of the dyebath is maintained at 35° C. for a further 15 minutes. The temperature is then raised to 60° C. over a period of 20 minutes. The temperature is maintained at 60° C. for a further 35 minutes. Rinsing is then carried out, followed by soaping at the boil for a quarter of an hour with a non-ionic detergent, rinsing again and drying.

Dyeing Procedure III

8 parts of the reactive dye obtained according to Example 26 are dissolved in 400 parts of water; 1400 parts of a solution containing 100 g of sodium sulfate per liter are added. 100 parts of cotton fabric are placed in the dyebath at 25° C. After 10 minutes, 200 parts of a solution containing 150 g of trisodium phosphate per liter are added. The temperature of the dyebath is then raised to 60° C. over a period of 10 minutes. The temperature is maintained at 60° C. for a further 90 minutes. Rinsing is then carried out, followed by soaping at the boil for a quarter of an hour with a non-ionic detergent, rinsing again and drying.

Dyeing Procedure IV

4 parts of the reactive dye obtained according to Example 26 are dissolved in 50 parts of water. 50 parts of a solution containing 5 g of sodium hydroxide and 20 g of calcined soda per liter are added. A cotton fabric is pad-dyed with the resulting solution to a weight gain of 70%, and is then wound onto a roll. The cotton fabric is stored in that form for 3 hours at room temperature. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing Procedure V

6 parts of the reactive dye obtained according to Example 26 are dissolved in 50 parts of water. 50 parts of a solution containing 16 g of sodium hydroxide and 0.04 liter of water glass (38°bé) per liter are added. A cotton fabric is pad-dyed with the resulting solution to a weight gain of 70%, and is then wound onto a roll. The cotton fabric is stored in that form for 10 hours at room temperature. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing Procedure VI

2 parts of the reactive dye obtained according to Example 26 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzene-sulfonate. A cotton fabric is impregnated with the resulting solution to a weight gain of 75% and is then dried. The fabric is then impregnated with a solution at 20° C. containing 4 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezed off to a 75% weight gain, and the dyeing is steamed for 30 seconds at from 100 to 102° C., rinsed, soaped for a quarter of an hour in a boiling 0.3% solution of a non-ionic detergent, rinsed and dried.

Printing Procedure I

While stirring rapidly, 3 parts of the reactive dye obtained according to Example 26 are sprinkled into 100 parts of a stock thickener containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate. The print paste so obtained is used to print a cotton fabric; drying is carried out and the resulting printed fabric is steamed in saturated steam at 102° C. for 2 minutes. The printed fabric is then rinsed, optionally soaped at the boil and rinsed again, and then dried.

Printing Procedure II

While stirring rapidly, 5 parts of the reactive dye obtained according to Example 26 are sprinkled into 100 parts of a stock thickener containing 50 parts of 5% sodium alginate thickener, 36.5 parts of water, 10 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 2.5 parts of sodium hydrogen carbonate. The print paste so obtained, the stability of which meets the technical requirements, is used to print a cotton fabric; drying is carried out and the resulting printed fabric is steamed in saturated steam at 102° C. for 8 minutes. The printed fabric is then rinsed, optionally soaped at the boil and rinsed again, and then dried. 

What is claimed is:
 1. A dye mixture comprising at least one dye of formula

wherein R₁ and R₂ are each independently of the other hydrogen or C₁-C₄alkyl, and D₁ and D₂ are each independently of the other a radical of formula (2)

 wherein (R₃)₀₋₃ denotes from 0 to 3 identical or different substituents selected from the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, nitro and sulfo, and X₁ is a radical of formula (3a), (3b), (3c), (3d), (3e) or (3f)  —SO₂—Z  (3a), —NH—CO—(CH₂)_(m)—SO₂—Z  (3b), —CONH—(CH₂)_(n)—SO₂—Z  (3c), —NH—CO—CH(Hal)-CH₂-Hal  (3d), —NH—CO—C(Hal)=CH₂  (3e) or

 wherein Y is halogen, T independently thereof has a meaning given for Y or is a non-fibre-reactive substituent or is a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e) —NH—(CH₂)₂₋₃—SO₂—Z  (4a), —NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂—Z  (4b),

 wherein Z is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions, Z′ is a group —CH(Hal)-CH₂-Hal or —C(Hal)=CH₂, m and n are each independently of the other the number 2, 3 or 4, and Hal is halogen, together with at least one dye of formula (8)

wherein r and s are each independently of the other the number 0 or 1, and X₂ and X₃ are each independently of the other a radical of formula (3a), (3b), (3c) or (3d) as given above.
 2. A dye mixture according to claim 1, wherein R₁ and R₂ are hydrogen.
 3. A dye mixture according to claim 1, wherein U is —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂.
 4. A dye mixture according to claim 1, wherein U is —Cl or —OSO₃H.
 5. A dye mixture according to claim 1, wherein D₁ and D₂ are each independently of the other a radical of formula (2a), (2b), (2c), (2d) or (2e)

wherein (R_(3a))₀₋₂ denotes from 0 to 2 identical or different substituents selected from the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, X_(1a) is α,β-dibromopropionylamino or α-bromoacryloylamino, m and n are each independently of the other the number 2 or 3, and Z₁, Z₂, Z₃ and Z₄ are each independently of the others vinyl, β-chloroethyl or β-sulfatoethyl.
 6. A dye mixture according to claim 1 comprising as the dye of formula (8) a dye of formula (8a), (8b) or (8c)

wherein one of the substituents G₁ and G₂ is amino and the other is hydroxy, X_(2a), X_(3a) and X_(3b) are each independently of the others β-sulfatoethylsulfonyl or vinylsulfonyl and X_(2b), X_(2c) and X_(3c) are each independently of the others α,β-dibromopropionylamino or α-bromoacryloylamino.
 7. A dye mixture according to claim 6 comprising a dye of formula (8a).
 8. A method for the dyeing or printing of hydroxyl-group-containing or nitrogen-containing fibre materials which comprises contacting said materials with a tinctorially effective amount of a dye mixture according to claim
 1. 9. A method according to claim 8, wherein cellulosic fibre materials are dyed or printed.
 10. A method according to claim 8, wherein cotton-containing fibre materials are dyed or printed. 